CN1077114C - Photosensitive resin composition for corrugated board printing plate - Google Patents
Photosensitive resin composition for corrugated board printing plate Download PDFInfo
- Publication number
- CN1077114C CN1077114C CN94190128A CN94190128A CN1077114C CN 1077114 C CN1077114 C CN 1077114C CN 94190128 A CN94190128 A CN 94190128A CN 94190128 A CN94190128 A CN 94190128A CN 1077114 C CN1077114 C CN 1077114C
- Authority
- CN
- China
- Prior art keywords
- resin composition
- weight
- liquid light
- printing forme
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
- C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
A liquid photosensitive resin composition used for producing a corrugated board printing plate comprising 100 parts by weight of an unsaturated polyurethane prepolymer (A) wherein the polyol segment comprises a polyether polyol, 17-200 parts by weight of an ethylenically unsaturated compound (B), and 0.01-10 parts by weight of a photopolymerization initiator (C), wherein the component (B) contains 17-65 parts by weight of an acrylate monomer represented by the general formula (I): CH2 = CH-CO-O-(C2H4O)n-R, per 100 parts by weight of the component (A).
Description
The present invention relates to a kind of liquid light maleate resin composition that on waved plate, prints with the elastic printing forme of HI high impact.This printing forme presses in the waved plate print field.
Printing forme material as the waved plate printing once used rubber, solid photosensitive resin and liquid light maleate resin.The printed material sheet that liquid light maleate resin is commonly used for the waved plate printing is because advantage economically, and promptly uncured resin can be recovered and re-use, and it can provide the works fine environment these characteristics, is to use the sheet material wash-out developer to carry out because develop.
The liquid light maleate resin composition that is used for being formed in the printing plate that prints on the waved plate generally comprises: prepolymer, alefinically unsaturated compounds and Photoepolymerizationinitiater initiater with ethylenical unsaturated double bonds.The printing forme that is used for the waved plate printing prepares by following steps: allow the liquid light maleate resin composition that actinic rays is carried out to image exposure (photocuring), carry out developing process then and handle post-exposure processing and drying treatment.
Being used for the important physical character that the printing plate of waved plate printing requires is bounce impact elasticity.The Japanese patent application publication No. of having examined 35481/1978 (being used to form the improvement photosensitive composition of flexographic printing plates) report, because waved plate has coarse and corrugated surface, the flexographic printing plates that is used for the waved plate printing with 35-45 degree soft (Shore A), intensity of outburst and excellent bounce impact elasticity is an ideal.
Unexamined European Patent Publication No 263366 (being used to print the photoresist printing forme of waved plate) discloses following content, when the photoresist plate that uses soft carried out the corrugated cardboard printing, existing paper scrap or analogue usually adhered on the surface of printing forme on the waved plate surface of supplying with printing press.Because in a single day paper scrap or analogue adhere to, then be difficult for coming off from the printing forme surface, in order to clean printing forme, need to interrupt the running of printing press.Thereby there is a very big practical problems in the photosensitive resin plate with soft, promptly reduced the throughput or the output of printed matter inevitably.In order to address this problem, need to reduce the surface viscosity of printing forme, improve the bounce impact elasticity of printing forme simultaneously.
As mentioned above, when the printing waved plate, need have the elastic printing forme of HI high impact.The condition of HI high impact rebound resilience printing forme is provided as the liquid light maleate resin composition, aforementioned unexamined European Patent Publication No No.263366 points out: (1) (i) preferably reduces ester bond, amido linkage and the amino-formate bond density of contained prepolymer in the liquid light maleate resin composition, because the existence of these keys trends towards reducing the bounce impact elasticity of gained photosensitive resin printing forme in the prepolymer.Especially (ii) when unsaturated polyurethanes is used as prepolymer, polyether glycol is an ideal and (iii) particularly as the polyvalent alcohol segment, when above unsaturated polyurethanes prepolymer has as polyvalent alcohol segmental 20% (weight) or more polytetramethylene glycol, obtained the elastic photosensitive resin printing forme of HI high impact.This part document is also pointed out: (2) as institute's substances containing ethylenically unsaturated compounds in the liquid light maleate resin composition, acrylate more can obtain the elastic photosensitive resin printing forme of HI high impact than methacrylic ester.Yet, the printing forme that does not still obtain having super bounce impact elasticity.It is not very good using the method (2) of acrylate, because acrylate exists outstanding toxicity problem and resulting printing forme to have lower mechanical property.
The invention provides a kind of liquid light maleate resin composition of the printing forme that on waved plate, prints.Do not change the hypotoxicity of said composition.Obtain from said composition by mask-making technology, be used for not had necessary mechanical property destroyed at the printing forme that waved plate prints, said composition has the bounce impact elasticity that increases.
The inventor finds, in being used for being formed on the liquid light maleate resin composition of the printing forme that prints on the waved plate, it comprises that polyether glycol is as polyvalent alcohol segmental unsaturated polyurethanes prepolymer, comprise that specified quantitative can reach above purpose as the composition of acrylate monomer alefinically unsaturated compounds, that have ad hoc structure, thereby finished the present invention.
That is to say that the invention provides a kind of liquid light maleate resin composition of the printing forme that prints on waved plate, said composition comprises:
(A) 100 weight parts contain the unsaturated polyurethanes prepolymer of polyether glycol as polyether segment,
(B) 17-200 weight part alefinically unsaturated compounds and
(C) 0.01-10 weight part Photoepolymerizationinitiater initiaters is characterized in that it comprises, based on 100 parts by weight of component (A) prepolymer, 17-65 weight parts by the acrylate monomer of following structural formula (I) expression as component (B) alefinically unsaturated compounds:
CH
2＝CH—CO—O—(C
2H
4O)
n—R (I)
N represents the number in 1-20 in the formula, and R represents to have the straight or branched alkyl of 2-22 carbon atoms.
The present invention will carry out following detailed description.
The unsaturated polyurethanes prepolymer of above component (A) is to react by the compound that allows polyether glycol, have 2 or more polyisocyanate-based polyisocyanates and comprise the functional group with active hydrogen and ethylenical unsaturated double bonds in molecule according to currently known methods to obtain.
Polyether glycol comprises polyoxyethylene glycol, polyoxypropylene diols, polyoxy tetramethylene glycol, polyoxyethylene-oxypropylene glycol is random or segmented copolymer, polyoxyethylene-oxygen tetramethylene glycol is random or segmented copolymer and polyoxypropylene-random or segmented copolymer of oxygen tetramethylene glycol.When the ratio of oxyethylene group group in the unsaturated polyurethanes prepolymer is 5% (weight) or when higher, the aqueous solution develops and is easy to carry out.
Polyisocyanates comprises tolylene diisocyanate, Xylene Diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl cyclohexane vulcabond and isophorone diisocyanate.
The functional group that has active hydrogen and ethylenical unsaturated double bonds in molecule comprises (methyl) Propylene glycol monoacrylate, (methyl) Hydroxyethyl acrylate and single (methyl) vinylformic acid polypropylene glycol ester.
With regard to the ratio of the isocyanate group of the hydroxyl of polyether glycol and polyisocyanates, require the amount of the latter's amount more than the former.Can be by changing the molecular weight that this ratio changes urethane.General use molecular-weight average is 5000-30000 urethane.
The alefinically unsaturated compounds of component (B) comprises (methyl) acrylic acid ester, for example, (methyl) alkyl acrylate is as (methyl) lauryl acrylate and (methyl) vinylformic acid octadecane ester, list (methyl) acrylate of (gathering) ethylene glycol or (gathering) propylene glycol, two (methyl) acrylate of (gathering) ethylene glycol or (gathering) propylene glycol, basic ester in three (methyl) acrylate of TriMethylolPropane(TMP) and (methyl) vinylformic acid are own.Since have 2 or more the polyenoid compound that belongs to unsaturated double-bond can increase the hardness of gained solidify material, must suitably use this compound, so that obtain the required hardness of solidify material.These alefinically unsaturated compounds can use separately or be used in combination according to purpose.The amount of these compounds is 17-200 parts (weight) based on 100 parts of (weight) prepolymers.
For the Photoepolymerizationinitiater initiater of component (C), can use usually at the employed initiator of ordinary light photosensitive resin composition.Photoepolymerizationinitiater initiater comprises ether such as the benzoin iso-propylether and the bitter almond oil camphor ethyl isobutyl ether of bitter almond oil camphor, and 2,2-dimethoxy-2-phenyl methyl phenyl ketone.According to the physical properties of the package stability of photosensitive resin composition, needed laser curing velocity and solidify material, these Photoepolymerizationinitiater initiaters can use separately or be used in combination.The amount of Photoepolymerizationinitiater initiater is 0.01-10 parts (weight) based on 100 parts of (weight) above prepolymers.
Acrylate monomer by structural formula (I) expression is that repeating unit is polyalkylene glycol monoalkyl ether and the acrylic acid ester of n.
Alefinically unsaturated compounds as component (B), main methacrylate monomer such as lauryl methacrylate(LMA), monomethyl vinylformic acid polypropylene glycol ester and the monomethyl vinylformic acid TEG ester of using, this is because they have hypotoxicity, and sheets thus obtained mechanical properties with excellence.Yet, not only contain the above liquid light maleate resin composition maintenance lower toxicity (this for liquid light maleate resin composition be important) of 17-65 weight parts (based on 100 weight part prepolymers) with the acrylate monomer of structural formula (I) expression, keep excellent mechanical property with the printing forme that obtains from this liquid light maleate resin composition, and the gained printing forme has the bounce impact elasticity of obvious raising.The result is that the waved plate printing can be carried out smoothly.Paper scrap or analogue can easily come off from the printing forme surface.In addition, liquid light maleate resin composition performance that must have such as low viscosity, package stability, egative film develop to the good replicability again of plate and the good aqueous solution and are not compromised.Performance such as ink resistance, the black absorptivity of seal and transitivity and weather resistance (must have these performances from the resulting printing forme of resin combination of the present invention by the technology that forms plate) are not compromised.
In the middle of various types of acrylate monomers such as benzyl acrylate, vinylformic acid phenoxy ethyl, modified acroleic acid nonylphenol ethylene oxide (propylene oxide) ester, isobornyl acrylate, vinylformic acid two ring pentyl ester, modified acroleic acid phthalic acid ethylene oxide (or propylene oxide) ester and modified acroleic acid succinate oxidation ethene (or propylene oxide) esters, the resulting printing forme of acrylate monomer by utilization structure formula (I) expression has the HI high impact rebound resilience.
With the consumption of the acrylate monomer of structural formula (I) expression,, be 17-65 weight parts based on 100 weight part prepolymers.When consumption is lower than 17 weight parts, can not on bounce impact elasticity, be significantly improved.When consumption is higher than 65 weight parts, can damage the replicability again of image and the physical strength of plate.For the obvious improvement that obtains bounce impact elasticity for example improves 10 hundred points and keeps from the good replicability again of the cured plate of liquid resin and the physical strength of plate, the consumption of the acrylate monomer of structural formula (I) expression is 30-60 weight parts preferably.In addition, when all monomers except that two functional groups or polyfunctional monomer (they are used for controlling the hardness of cured plate) are replaced by the acrylate monomer of structural formula (I), more can improve bounce impact elasticity effectively.
N in the structural formula (I) represents the repeat number 1-20 of oxyethylene group group.N is big more, and bounce impact elasticity is high more.Yet, when n becomes big, become insufficient by the effect (dilution effect) of the reduction resin combination viscosity that Acrylic Acid Monomer gave of structural formula (I) expression, and reduced anti-aniline water-based seal performance of ink.In view of these aspects, n preferably is no more than 20.Consider the balance between bounce impact elasticity, dilution effect and the anti-seal China ink, n is more preferably 2-10.
R is the straight or branched alkyl with 2-22 carbon atoms.Alkyl comprises ethyl, propyl group, butyl, amyl group, octyl group, iso-octyl, decyl, isodecyl and 2-ethylhexyl.When R was methyl, wherein carbonatoms was 1, and the gained printing forme certainly will have lower water resisting property seal performance of ink.When the carbonatoms of alkyl surpasses 22, reduced dilution effect to resin combination.In order to improve dilution effect, R preferably has the alkyl of 2-14 carbon atoms.
Specific examples by the acrylate monomer of structural formula (I) expression is a vinylformic acid glycol ethyl ether ester, vinylformic acid ethylene glycol butyl ether ester, vinylformic acid Diethylene Glycol-2-ethylhexyl ether-ether, vinylformic acid nine ethylene glycol lauryl ether-ethers and vinylformic acid triethylene glycol hexyl ether-ether.They can separately or be used in combination.
If desired, according to purpose, additive such as photostabilizer, oxidation inhibitor, lubricant, dyestuff and pigment can be added in this photosensitive resin composition.
In order to use liquid light maleate resin composition of the present invention to make the printing forme that is used on waved plate, printing, generally to carry out following steps.
Egative film is placed on the sheet glass, covers thin protective film.Be poured onto on the protective film so that when this resin combination has constant thickness, on the resin combination of being toppled over, formed the carrier counterdie at liquid light maleate resin composition of the present invention.Sheet glass is placed on the bed die so that the liquid light maleate resin composition layer has predetermined constant thickness.Then, carry out the short period of time exposure with actinic rays source, top.Then, carry out back-exposure and form even thin resin layer, be i.e. bottom on the carrier total area of plate.Form burr by being carried out to image exposure with low light level ray.Uncured resin is washed out and is removed (development).In whole sheets thus obtained immersion water, then further to actinic rays exposure (post-exposure in water), with the plate completely solidified.Obtain being used for printing the printing forme of waved plate by the completely crued plate of drying.
Measure bounce impact elasticity of the present invention according to falling sphere method (20 ℃).Allow the iron ball of 8mm diameter be on the model of 7mm at thickness by gravity fall from the height of 30cm.Then, measure the height on plate (Scm) that rebounds and reached on the ball slave plate.Bounce impact elasticity (%) is determined by following equation:
Bounce impact elasticity (%)=100 * (S/30)
In this measuring method, if there is any surface viscosity in model, then the observed value of bounce impact elasticity changes.Therefore, the powdered processing is carried out on the model surface with talcum or analogue after, measure again.
Describe the present invention in detail below with reference to embodiment and comparative example.
The comparative example 1
(based on the embodiment 1 of unexamined European Patent Publication No No.263366)
2000) and 1mol polytetramethylene glycol (number-average molecular weight 2000) and obtained having the urethane polymer of isocyanate group then 80 ℃ of reactions in 2 hours by 2.4 moles of toluene diisocyanate and 20ppm dibutyl tin laurate being joined 1mol polypropylene glycol (number-average molecular weight: at two end groups.Then, by in urethane polymer, adding 2.0mol monomethyl vinylformic acid polypropylene glycol ester, allow them react absorption peak (the about 2260cm that belongs to isocyanate group up on infrared spectra, almost not observing then
-1) till, obtain the unsaturated polyurethanes prepolymer.
With 26 weight part lauryl methacrylate(LMA)s, 17 weight part monomethyl vinylformic acid TEG monomethyl ether-ethers, 2.1 weight part dimethacrylate TEG ester, 1.4 weight part trihydroxy methyl propane trimethyl acrylate, 1.0 weight part 2,2-dimethoxy-2-phenyl methyl phenyl ketone and 0.7 weight part 2,6-di-t-butyl-right-cresylol joins in the 100 weight part prepolymers, then they is dissolved in the prepolymer, obtains the liquid light maleate resin composition.
Gained liquid light maleate resin composition is not having problems aspect viscosity number and the package stability, with the common liq photosensitive resin composition of the printing forme that is used for making the printing waved plate comparatively speaking (for example: APR F-47, make) by chemical industry company limited of Asahi Chemical Industry.
For by using the liquid light maleate resin composition to obtain the printing forme of thickness, can carry out following processing: become image exposure (mask exposure: 5 minutes as 7mm; Burr exposure: 4 minutes; Backside exposure: 40 seconds) be to use exposure apparatus (the ALF type is made by chemical industry company limited of Asahi Chemical Industry) to carry out.Then, by spray the developing solution that contains 2% tensio-active agent (W-8 is made by chemical industry company limited of Asahi Chemical Industry) with washing device (AL-400W type, by chemical industry company limited of Asahi Chemical Industry make) with uncured part flush away.Then, plate is immersed in the water, then by using post-exposure device (ALF-200UP type is made by chemical industry company limited of Asahi Chemical Industry) to be exposed to the UV-light of chemical lamp simultaneously and the UV-light of germicidal lamp reaches 10 minutes.Subsequently, the plate that is exposed to UV-light is following dry 15 minutes at 60 ℃.
The value of sheets thus obtained bounce impact elasticity is 35%.This liquid light maleate resin composition is out of question aspect the replicability again of plate and aqueous solution development at egative film, the gained printing forme is being out of question aspect physical strength, water resisting property seal performance of ink, the black absorptivity of seal and transfer ability and the weather resistance, this be the printing forme that obtains with the common liq photosensitive resin composition of the printing forme that is used for making the printing waved plate (for example: APR F-47, make) with from it by chemical industry company limited of Asahi Chemical Industry comparatively speaking.
Embodiment 1 and 2
According to the method same with comparative example 1, just whole consumptions of 17 weight part list vinylformic acid TEG monomethyl ether-ethers are changed into 17 parts by weight of acrylic acid Diethylene Glycols-2-ethylhexyl ether-ether, obtain the printing forme that liquid light maleate resin composition and thickness are 7mm.The bounce impact elasticity of gained printing forme is 43% (embodiment 1).
According to the method same with comparative example 1, just the consumption (43 weight part) of monomethyl vinylformic acid TEG monomethyl ether ester and lauryl methacrylate(LMA) is changed into 43 parts by weight of acrylic acid Diethylene Glycols-2-ethylhexyl ether-ether, obtains the printing forme that liquid light maleate resin composition and thickness are 7mm.The bounce impact elasticity of gained printing forme is 57% (embodiment 2).
The viscosity number of resulting liquid light maleate resin composition and package stability identical with comparative example 1 almost in embodiment 1 and 2.Egative film develops to the aqueous solution of the replicability again of plate and liquid light maleate resin composition, and the physical strength of embodiment 1 and 2 gained printing formes, water resisting property seal performance of ink, the black absorptivity of seal and transitivity and weather resistance identical with comparative example 1 almost.Thereby this liquid light maleate resin composition is out of question at above aspect of performance.
In order to confirm that the printing forme surface that paper scrap or analogue can easily obtain comes off, and prints test with the actual print machine under the following conditions from embodiment 2.
Printing press: 3FM-84 (three-colour printing machine) is had by Mitsubishi (Mitsubishi) heavy industry
Limit company makes.
Yin Mo: DF-140, ultramarine blue aniline water-based seal China ink is made by Sakata Inx Corp..
Seal speed: 250/minute.
Waved plate: the B concave surface (size: 125cm * 75cm)
Waved plate number: 5000.
In printing process, when finding the waved plate of printing defects is arranged, need to interrupt the running of printing press, so that the eccysis that uses cloth to wipe with removes to stick to the paper scrap that plate is opened.The evaluation that removes performance to paper scrap or analogue is to carry out according to the number of times that interrupts printing press.
During the printing forme that obtains in using embodiment 2, the printing of waved plate can be carried out well, and does not interrupt.
During the printing forme that obtains in using comparative example 1, the number of times that interrupts printing press is 10 times.
Embodiment 3-7
According to the method same with comparative example 1, just total consumption (43 weight part) of monomethyl vinylformic acid TEG monomethyl ether-ether and lauryl methacrylate(LMA) is changed into 43 weight parts each acrylate monomer by the structural formula shown in the table 1 (I) expression in each embodiment, obtains the liquid light maleate resin composition and has the printing forme that thickness is 7mm.
The bounce impact elasticity numerical value of gained printing forme is shown in table 1.
Table: 1
| Embodiment | (I) acrylate monomer of structural formula (I) expression | n | The carbonatoms of R | Bounce impact elasticity (%) |
| 2 3 4 5 6 7 | Acrylic acid diethylene glycol-2-ethyl ether-ether acrylic acid diethylene glycol ethyl ether-ether acrylic acid TEG-2-ethylhexyl ether-ether acrylic acid, eight ethylene glycol-2-ethylhexyl ether-ether acrylic acid, nine ethylene glycol tridecyl ether-ether acrylic acid triethylene glycol hexyl ether-ethers | 2 2 4 8 9 3 | 8 2 8 8 13 6 | 57 57 60 61 59 62 |
The viscosity number of the liquid light maleate resin composition that obtains in embodiment 3-7 and package stability be just the same with embodiment 2 almost.Egative film is to the replicability again of plate and the aqueous solution developing performance of this liquid light maleate resin composition, and the physical strength of the printing forme that in embodiment 3-7, obtains, water resisting property seal performance of ink, the black absorptivity of seal and transitivity and weather resistance identical with embodiment 2 almost.Thereby this liquid light maleate resin composition is out of question in above performance.
The comparative example 2
By 3.4mol tolylene diisocyanate and 20ppm dibutyl tin laurate are joined 1mol polyoxyethylene-oxypropylene glycol segmented copolymer dibasic alcohol (number-average molecular weight: 2500,1/4) and 2.1mol polytetramethylene glycol dibasic alcohol (number-average molecular weight: 1200) weight ratio of ethylene oxide and propylene oxide:, allow them react 2 hours down then, obtain having the urethane polymer of isocyanate group at two end groups at 80 ℃.Then, by with 4.9mol monomethyl vinylformic acid polypropylene glycol ester (molecular weight: 380) join in the urethane polymer, allow then their the reaction up on infrared spectra, almost do not observe belong to isocyanate group absorption peak (at 2260cm
-1Near) till, obtain the unsaturated polyurethanes prepolymer.The weight percent of ethylene oxide is about 9% in the unsaturated polyurethanes prepolymer.
With 26 weight part lauryl methacrylate(LMA)s, 17 weight part monomethyl vinylformic acid TEG monomethyl ether-ethers, 2.1 weight part dimethacrylate TEG esters, 1.4 weight part trimethylammonium vinylformic acid trimethylolpropene esters, 1.0 weight 2,2-dimethoxy-2-phenyl methyl phenyl ketone and 0.7 weight part 2,6-di-t-butyl-right-methylphenol joins in the 100 weight part prepolymers, yet be dissolved in the prepolymer by mixing, obtain the liquid light maleate resin composition.
Gained liquid light maleate resin composition is out of question aspect viscosity number or package stability, with the common liq photosensitive resin composition that is used for being formed in the printing forme that prints on the waved plate (for example: APR F-47, make) by chemical industry company limited of Asahi Chemical Industry comparatively speaking.
Obtain the printing forme of thickness by using as 7mm according to liquid light maleate resin composition with the same method of comparative example 1.
Sheets thus obtained bounce impact elasticity numerical value is 34%.This liquid light maleate resin composition is out of question aspect the replicability again of plate or aqueous solution development at egative film, the gained printing forme is being out of question aspect physical strength, water resisting property seal performance of ink, the black absorptivity of seal and transitivity or the weather resistance, the photosensitive printing forme that obtains to oil/fat composition (for example: APR F-47, made by chemical industry company limited of Asahi Chemical Industry) with from it of this common liq with the printing forme that is used for making the printing waved plate comparatively speaking.
Embodiment 8 and 9
According to comparative example 2 with the methods of producing, just total consumption (17 weight part) of monomethyl vinylformic acid TEG monomethyl ether is changed into 17 parts by weight of acrylic acid Diethylene Glycols-2-ethylhexyl ether-ether, and the seal that obtains liquid light maleate resin composition and thickness and be 7mm is anti-.Sheets thus obtained bounce impact elasticity is 42% (embodiment 8).
According to the method same with comparative example 2, just the total amount (43 weight part) of monomethyl vinylformic acid TEG monomethyl ether-ether and lauryl methacrylate(LMA) is changed into 43 parts by weight of acrylic acid Diethylene Glycols-2-ethylhexyl ether-ether, obtains the printing forme that liquid light maleate resin composition and thickness are 7mm.The bounce impact elasticity of gained printing forme is 52% (embodiment 9).
The viscosity number of the liquid light maleate resin composition that obtains in embodiment 8 and 9 and package stability be identical with comparative example 2 almost.Egative film is to the replicability again of plate and the aqueous solution developing performance of liquid light maleate resin composition, and in physical strength, water resisting property seal performance of ink, the black absorptivity of seal and the transitivity of embodiment 8 and 9 gained printing formes and weather resistance identical with comparative example 2 almost.Therefore, this liquid light maleate resin composition is out of question at above aspect of performance.
Commercial Application
Liquid light maleate resin composition of the present invention comprises the acrylate monomer with ad hoc structure of specified quantitative. When using this liquid light maleate resin composition to make at the printing forme that corrugated plating prints, the gained printing forme has the bounce impact elasticity of raising. When using this plate to carry out the corrugated plating printing, can print well, and paper scrap or analog easily come off on the slave plate surface.
Claims (4)
1. liquid light maleate resin composition that is used for being formed in the printing forme that prints on the waved plate, it comprises:
(A) to have polyether glycol be the unsaturated polyurethanes prepolymer of 5000-30000 as polyvalent alcohol segmental molecular-weight average to 100 weight parts,
(B) 17-200 weight part alefinically unsaturated compounds and
(C) 0.01-10 weight part Photoepolymerizationinitiater initiaters.
It is characterized in that it comprises, based on the prepolymer of 100 parts by weight of component (A), 17-65 weight parts by the acrylate monomer of following structural formula (I) expression as component
(B) alefinically unsaturated compounds:
CH
2＝CH—CO—O—(C
2H
4O)
n—R (I)
N represents the number in 1-20 in the formula, and R represents to have the straight or branched alkyl of 2-22 carbon atoms.
2. according to the liquid light maleate resin composition of claim 1, wherein the amount by the acrylate monomer of structural formula (I) expression is 30-60 weight parts.
3. according to the liquid light maleate resin composition of claim 1 or 2, wherein the middle n of structural formula (I) represents the number in 2-10.
4. according to the liquid light maleate resin composition of claim 1 or 2, wherein the middle R of structural formula (I) represents to have the straight or branched alkyl of 2-14 carbon atoms.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17086793 | 1993-06-18 | ||
| JP170867/93 | 1993-06-18 | ||
| JP170867/1993 | 1993-06-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1107278A CN1107278A (en) | 1995-08-23 |
| CN1077114C true CN1077114C (en) | 2002-01-02 |
Family
ID=15912789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94190128A Expired - Fee Related CN1077114C (en) | 1993-06-18 | 1994-06-16 | Photosensitive resin composition for corrugated board printing plate |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5716757A (en) |
| EP (1) | EP0656378B1 (en) |
| CN (1) | CN1077114C (en) |
| AU (1) | AU675552B2 (en) |
| ES (1) | ES2080027B1 (en) |
| GB (1) | GB2283244B (en) |
| WO (1) | WO1995000567A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018932A1 (en) * | 1994-12-13 | 1996-06-20 | Macdermid Imaging Technology, Inc. | Photosensitive compositions and clean running photopolymer printing plates therefrom |
| US5965460A (en) * | 1997-01-29 | 1999-10-12 | Mac Dermid, Incorporated | Polyurethane composition with (meth)acrylate end groups useful in the manufacture of polishing pads |
| JP2003277453A (en) * | 2002-03-27 | 2003-10-02 | Jsr Corp | Liquid curable resin composition |
| JP4093557B2 (en) * | 2002-11-14 | 2008-06-04 | 東洋合成工業株式会社 | Photosensitive resin composition, method for forming hydrogel, and hydrogel |
| JP5214467B2 (en) | 2006-12-26 | 2013-06-19 | 旭化成イーマテリアルズ株式会社 | Resin composition for printing plate |
| WO2008125200A1 (en) * | 2007-04-11 | 2008-10-23 | Bayer Materialscience Ag | Radiation-crosslinking and thermally crosslinking pu systems based on isocyanate-reactive block copolymers |
| CN101945905B (en) * | 2008-02-15 | 2013-06-26 | 旭化成电子材料株式会社 | Resin composition |
| KR102665293B1 (en) | 2019-04-01 | 2024-05-09 | 주식회사 엘지화학 | Antibacterial polymer coating composition and antibacterial polymer film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0263366A2 (en) * | 1986-10-02 | 1988-04-13 | Asahi Kasei Kogyo Kabushiki Kaisha | A photoresin printing plate for use in printing a corrugated board |
| EP0427950A2 (en) * | 1989-11-16 | 1991-05-22 | Asahi Kasei Kogyo Kabushiki Kaisha | A photosensitive resin composition for use in forming a relief structure |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS527363B2 (en) * | 1973-05-21 | 1977-03-02 | ||
| US3960572A (en) * | 1973-02-21 | 1976-06-01 | Asahi Kasei Kogyo Kabushiki Kaisha | Photosensitive compositions comprising a polyester-polyether block polymer |
| JPS5335481B2 (en) * | 1974-04-08 | 1978-09-27 | ||
| JPS5921541B2 (en) * | 1977-05-18 | 1984-05-21 | 東洋紡績株式会社 | Photosensitive resin composition for printing plates |
| US4298630A (en) * | 1978-03-23 | 1981-11-03 | Northern Telecom Ltd. | Method of manufacturing electrically insulated conductors with ultra-violet cured coatings |
| US4932750A (en) * | 1982-12-09 | 1990-06-12 | Desoto, Inc. | Single-coated optical fiber |
| JPS6121118A (en) * | 1984-07-10 | 1986-01-29 | Yokohama Rubber Co Ltd:The | Photosetting resin composition |
| US5288571A (en) * | 1986-10-02 | 1994-02-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Photoresin printing plate for use in printing a corrugated board |
| US4854666A (en) * | 1987-02-04 | 1989-08-08 | Mitsui Toatsu Chemicals, Incorporated | Photosetting resin composition |
| JP2944164B2 (en) * | 1990-08-08 | 1999-08-30 | 旭化成工業株式会社 | Liquid photosensitive resin composition for flexographic printing plates |
| JPH05301935A (en) * | 1992-04-28 | 1993-11-16 | Sekisui Chem Co Ltd | Photocurable resin composition |
-
1994
- 1994-06-16 US US08/325,405 patent/US5716757A/en not_active Expired - Lifetime
- 1994-06-16 WO PCT/JP1994/000974 patent/WO1995000567A1/en active IP Right Grant
- 1994-06-16 EP EP94918531A patent/EP0656378B1/en not_active Expired - Lifetime
- 1994-06-16 AU AU69820/94A patent/AU675552B2/en not_active Ceased
- 1994-06-16 CN CN94190128A patent/CN1077114C/en not_active Expired - Fee Related
- 1994-06-16 GB GB9422035A patent/GB2283244B/en not_active Expired - Lifetime
- 1994-12-09 ES ES09450032A patent/ES2080027B1/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0263366A2 (en) * | 1986-10-02 | 1988-04-13 | Asahi Kasei Kogyo Kabushiki Kaisha | A photoresin printing plate for use in printing a corrugated board |
| EP0427950A2 (en) * | 1989-11-16 | 1991-05-22 | Asahi Kasei Kogyo Kabushiki Kaisha | A photosensitive resin composition for use in forming a relief structure |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0656378B1 (en) | 1999-12-08 |
| AU675552B2 (en) | 1997-02-06 |
| GB2283244A (en) | 1995-05-03 |
| GB9422035D0 (en) | 1995-03-01 |
| ES2080027B1 (en) | 1996-08-01 |
| EP0656378A4 (en) | 1997-12-29 |
| AU6982094A (en) | 1995-01-17 |
| GB2283244B (en) | 1997-08-13 |
| CN1107278A (en) | 1995-08-23 |
| EP0656378A1 (en) | 1995-06-07 |
| US5716757A (en) | 1998-02-10 |
| WO1995000567A1 (en) | 1995-01-05 |
| ES2080027A1 (en) | 1996-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1078357C (en) | Waterborne photoresists having associate thickeners | |
| CN1077114C (en) | Photosensitive resin composition for corrugated board printing plate | |
| US6214522B1 (en) | Photosensitive resin composition useful in fabricating printing plates | |
| CN101057181A (en) | Photosensitive resin composition for flexographic printing | |
| WO2007052470A1 (en) | Lithographic printing plate material, lithographic printing plate, method for preparing lithographic printing plate, and method for printing by lithographic printing plate | |
| JP2644898B2 (en) | Photosensitive resin composition for forming relief | |
| US4209582A (en) | Method of preparing screen printing stencils using novel compounds and compositions | |
| JPS5869235A (en) | Syndiotactic polybutadiene composition for flexographic plate | |
| EP0263366B1 (en) | A photoresin printing plate for use in printing a corrugated board | |
| JP2532291B2 (en) | No dampening water required Photosensitive lithographic printing plate | |
| CN100529971C (en) | Process for producing water development printing plate for relief printing | |
| US4254194A (en) | Screen printing stencils using novel compounds and compositions | |
| US4286048A (en) | Photocrosslinkable compositions for screen printing stencils | |
| US4276367A (en) | Method of preparing lithographic printing plates using novel compounds and compositions, and improved lithographic printing plates | |
| JP2008250055A (en) | Photosensitive resin composition and photosensitive resin original printing plate using the same | |
| JP3371927B2 (en) | Liquid photosensitive resin composition for producing printing plate for corrugated ball printing | |
| CN1072812C (en) | Waterborne photoresists having polysiloxanes | |
| CN1347929A (en) | Photosensitive resin composition for producing printing board | |
| CN112955820A (en) | Water developable flexographic printing original plate | |
| JP2005326722A (en) | Multilayer flexographic printing plate and method for making same | |
| JP2008058957A (en) | Photosensitive resin composition and photosensitive resin printing original plate using the same | |
| JP3835867B2 (en) | Liquid photosensitive resin composition for printing plate manufacturing | |
| JP2004341286A (en) | Method for manufacturing liquid photosensitive resin relief printing plate | |
| WO1995012146A1 (en) | Dry lithographic forme | |
| CA1103085A (en) | Photopolymerizable compositions containing a liquid unsaturated polyester and a liquid urethane polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Applicant after: Asahi Kasei Kogyo K. K. Applicant before: Asahi Kasei Kogyo K. K. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: ASAHI KASEI CORPORATION TO: ASAHI KASEI CORPORATION |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ASAHI KASEI ELECTRONICS MATERIALS CO., LTD. Free format text: FORMER OWNER: ASAHI KASEI CORPORATION Effective date: 20091016 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20091016 Address after: Tokyo, Japan Patentee after: Asahi Chemical Corp. Address before: Osaka Japan Patentee before: Asahi Kasei Kogyo K. K. |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20020102 Termination date: 20100616 |